CN108172782B - Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure - Google Patents

Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure Download PDF

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CN108172782B
CN108172782B CN201711329542.3A CN201711329542A CN108172782B CN 108172782 B CN108172782 B CN 108172782B CN 201711329542 A CN201711329542 A CN 201711329542A CN 108172782 B CN108172782 B CN 108172782B
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carbon
shell
coated porous
cobaltous oxide
core structure
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CN108172782A (en
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李丹
苏行
董玉涛
马宇航
张建民
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Zhengzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a simple method for preparing a carbon-coated porous cobaltous oxide nano material with a shell-core structure and electrochemical performance of the carbon-coated porous cobaltous oxide nano material as an anode of a lithium ion battery, and the specific preparation steps comprise: preparing a solid cobaltosic oxide nanocube by a hydrothermal method; after the surface of the prepared nanocube is coated with PDA, the carbon-coated porous cobaltous oxide shell-core nanomaterial is obtained by medium-high temperature calcination, and finally the carbon-coated porous cobaltous oxide nanomaterial with the shell-core structure is formed by hydrochloric acid etching. The method does not add any directing agent and surfactant, has mild conditions, environmental protection, cheap raw materials and low requirement on equipment in the whole synthesis process, is convenient for industrial production, and has great application prospect in the preparation of the anode material of the lithium ion battery.

Description

Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure
Technical Field
The invention relates to a synthesis method for preparing a carbon-coated porous cobaltous oxide nano material with a shell-core structure and application of the carbon-coated porous cobaltous oxide nano material in a power lithium ion battery anode.
Background
With the continuous development of the technology and the gradual change of life style of people, the lithium ion battery has more and more prominent position in life, and the demand of people for electrode materials with high rate performance is more and more urgent. As a negative electrode material of a lithium ion battery, the theoretical specific capacity of cobaltous oxide is up to 715mAh g-1About 2 times as much as graphitized carbon. But the first coulombic efficiency and the cycle performance of cobaltous oxide are poor. To overcome these disadvantages, the structural design of cobaltous oxide is especially important, for example, Chinese patent document CN 103950994B adopts organic metal cobalt salt and two kinds of cobalt saltsThe protective agent finally synthesizes the double-layer cobaltous oxide hollow nano-particles through solvothermal reaction; K.J.an and N.Y.Lee et al adopt cobalt chloride hexahydrate as a raw material to synthesize cobaltous oleate, and then decompose the cobaltous oleate through high-temperature thermal decomposition to finally prepare a CoO nanorod (J.Am.chem.Soc.2006,128, 9753-9760); chinese patent document CN 101800302 a invented graphene nanosheet-cobaltous oxide composite negative electrode material synthesized by hydrothermal reaction. At present, few reports are made on carbon-coated porous cobaltous oxide nanocube three-dimensional materials with shell-core structures, so that the materials have practical significance and application value for research and development.
Disclosure of Invention
The invention aims to provide a synthesis method for synthesizing a carbon-coated porous cobaltous oxide nano material with a shell-core structure and application of the carbon-coated porous cobaltous oxide nano material to a lithium ion battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a carbon-coated porous cobaltous oxide nano material with a shell-core structure comprises the following steps:
firstly, preparing cobaltosic oxide nano material by using hydrothermal method
Dispersing cobalt nitrate hexahydrate in deionized water, magnetically stirring until the cobalt nitrate hexahydrate is transparent, adding sodium hydroxide into the solution, continuously stirring until the cobalt nitrate hexahydrate is transparent, transferring the obtained solution into a reaction kettle, reacting for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, centrifuging, centrifugally washing the obtained solid for a plurality of times by using an ethanol water solution, and drying the centrifuged solid to obtain a cobaltosic oxide nano material;
secondly, coating the surface of the cobaltosic oxide nano material prepared in the first step with PDA
Dissolving the cobaltosic oxide nano material prepared in the first step and dopamine hydrochloride in a tris (hydroxymethyl) aminomethane buffer solution, stirring for 3h at room temperature, centrifuging, centrifugally washing the obtained solid with an ethanol aqueous solution for several times, and drying the centrifuged solid to obtain the cobaltosic oxide nano material with the surface coated with PDA;
thirdly, calcining the material obtained in the second step to obtain the carbon-coated porous cobaltous oxide nano material with the shell-core structure
The calcining condition is that the cobaltosic oxide nano material with the surface wrapped by the PDA obtained in the second step is kept at the constant temperature of 450-500 ℃ for 2-4 h at the heating rate of 5 ℃/min.
Preferably, the method also comprises a fourth step of hydrochloric acid etching, wherein the carbon-coated porous cobaltous oxide nano material obtained in the third step is soaked in a hydrochloric acid solution for 12min or less, then washed with an ethanol water solution for a plurality of times, centrifuged, and then the solid is dried in vacuum to obtain the carbon-coated porous cobaltous oxide nano material with the shell-core structure.
Preferably, the mass ratio of the cobalt nitrate hexahydrate to the sodium hydroxide in the first step is 4: 1.
Preferably, the concentration of the tris (hydroxymethyl) aminomethane buffer in the second step is 10 mM.
Preferably, the concentration of cobaltosic oxide in the second step is 0.9g/ml, and the concentration of dopamine hydrochloride in the second step is 0.4 g/ml.
Preferably, the concentration of the hydrochloric acid solution in the fourth step is 0.1 mol/L.
The carbon-coated porous cobaltous oxide nano material prepared by the preparation method of the carbon-coated porous cobaltous oxide nano material with the shell-core structure is applied to a lithium ion battery as a negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon-coated porous cobaltous oxide nanocube three-dimensional material prepared by the preparation method has a shell-core structure, the structure has a plurality of mesopores, and the transmission path of lithium ions and electrons can be effectively improved, so that the multiplying power performance of the material is improved; secondly, the carbon coated outside can effectively prevent the capacity from being attenuated due to the direct contact of the electrolyte and the active material.
2. The whole process of the invention is carried out in a water system, no guiding agent and surfactant are added, and the preparation process is simple, green, cheap and safe, and is easier to realize industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1;
FIG. 2 is a scanning electron micrograph of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1;
FIG. 3 is a transmission electron micrograph of the carbon-coated porous cobaltous oxide nanomaterial with the shell-core structure prepared in example 1;
FIG. 4 is a transmission electron micrograph of a carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure obtained by etching for 3 minutes in example 2;
FIG. 5 is a transmission electron micrograph of a carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure obtained by etching for 6 minutes in example 3;
FIG. 6 is a transmission electron micrograph of a carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure obtained by etching for 12 minutes in example 4;
FIG. 7 is a cyclic voltammogram of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1;
fig. 8 is a cycle chart of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1 as an electrode material under different current densities.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The preparation method of the carbon-coated porous cobaltous oxide nano material with the shell-core structure comprises the following steps:
first, preparation of cobaltosic oxide nanocubes
Preparing cobaltosic oxide by a hydrothermal method (also called hydrothermal method), dispersing 0.04 mol of cobalt nitrate hexahydrate in 40 mL of deionized water, and stirring the mixture under magnetic stirring until the mixture is transparent; adding 0.01 mol of sodium hydroxide into the solution, and continuously stirring the solution until a clear solution is obtained; transferring the solution into a 50 mL polytetrafluoroethylene reaction kettle, and placing the reaction kettle in an oven to react for 24 hours at 180 ℃; after the reaction is finished, naturally cooling the reaction kettle to room temperature, centrifugally separating the obtained sample, centrifugally washing the sample for three times by using a water/ethanol mixed solution, and drying the sample for 12 hours at 65 ℃;
second, preparation of PDA (polydopamine) -wrapped cobaltosic oxide nanocubes
Putting 90 mg of cobaltosic oxide prepared in the first step and 40 mg of dopamine hydrochloride into 100 mL of 10mM Tris-buffer solution, and stirring for 3h at room temperature; then centrifugally separating the precipitate, centrifugally washing the precipitate for three times by using a water/ethanol mixed solution, and drying the precipitate for 12 hours at 65 ℃;
step three, preparing the porous carbon-coated cobaltous oxide by temperature control conversion
And (3) putting the product prepared in the second step into a tubular furnace, heating at the speed of 5 ℃/min, and keeping the temperature at the temperature of 500 ℃ for 3 hours to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with the shell-core structure.
The XRD pattern of the carbon-coated cobaltous oxide material prepared in this example is shown in fig. 1, and compared with a standard card, the carbon-coated cobaltous oxide material prepared in this example is illustrated. The scanning electron microscope image and the transmission electron microscope image are shown in FIGS. 2 and 3.
Example 2
As in example 1, except that,
fourthly, preparation of porous carbon-coated cobaltous oxide by hydrochloric acid etching
And dispersing the product prepared in the third step in a hydrochloric acid solution with the concentration of 0.1mol/L for etching for 3min, then washing with deionized water/ethanol to remove soluble impurities, centrifugally separating the obtained substance, and drying in vacuum at 65 ℃ to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure.
The transmission electron microscope image of the carbon-coated porous cobaltous oxide nanocube three-dimensional material etched by hydrochloric acid in the embodiment is shown in fig. 4.
Example 3
As in example 1, except that,
fourthly, preparation of porous carbon-coated cobaltous oxide by hydrochloric acid etching
And dispersing the product prepared in the third step in a hydrochloric acid solution with the concentration of 0.1mol/L for etching for 6min, then washing by deionized water/ethanol to remove soluble impurities, centrifugally separating the obtained substance, and drying in vacuum at 65 ℃ to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure.
The transmission electron microscope image of the carbon-coated porous cobaltous oxide nanocube three-dimensional material etched by hydrochloric acid in the embodiment is shown in fig. 5.
Example 4
As in example 1, except that,
fourthly, preparation of porous carbon-coated cobaltous oxide by hydrochloric acid etching
And dispersing the product prepared in the third step in a hydrochloric acid solution with the concentration of 0.1mol/L for etching for 12min, then washing with deionized water/ethanol to remove soluble impurities, centrifugally separating the obtained substance, and drying in vacuum at 65 ℃ to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure.
The transmission electron microscope image of the carbon-coated porous cobaltous oxide nanocube three-dimensional material etched by hydrochloric acid in the embodiment is shown in fig. 6.
The process for preparing the carbon-coated porous cobaltous oxide nanocube three-dimensional material has the advantages of simple requirement on the whole reaction condition, low cost, greenness and environmental protection, and is more suitable for industrial production. The X-ray diffraction pattern of the prepared carbon-coated porous cobaltous oxide nanocube material with the shell-core structure is shown in figure 1, and the sample is single-phase cobaltous oxide (JCPDS: 48-1719). FIG. 2 is an SEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1, wherein the cobaltous oxide surface is uniformly coated with a carbon layer and has obvious holes; FIG. 3 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1; FIG. 4 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure obtained by 3min etching; FIG. 5 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure obtained by 6min etching; FIG. 6 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure obtained by 12min etching, wherein the cobaltous oxide inside is completely etched, and only a carbon shell is left; FIG. 7 shows a cyclic voltammogram of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1; FIG. 8 shows the electrochemical cycle diagram of the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1 at the current density of 0.2A/g.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (1)

1. A preparation method of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure for improving the multiplying power performance of a lithium ion battery cathode material is characterized by comprising the following steps:
firstly, preparing cobaltosic oxide nanocubes by using a hydrothermal method
Dispersing cobalt nitrate hexahydrate in deionized water, magnetically stirring until the cobalt nitrate hexahydrate is transparent, adding sodium hydroxide into the solution, continuously stirring until the cobalt nitrate hexahydrate is transparent, transferring the obtained solution into a reaction kettle, reacting for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, centrifuging, centrifugally washing the obtained solid for a plurality of times by using an ethanol water solution, and drying the centrifuged solid to obtain a cobaltosic oxide nanocube;
secondly, coating the surface of the cobaltosic oxide nano cube prepared in the first step with PDA
Dissolving the cobaltosic oxide nanocube prepared in the first step and dopamine hydrochloride in 10mM tris (hydroxymethyl) aminomethane buffer solution, stirring for 3h at room temperature, centrifuging, centrifugally washing the obtained solid with an ethanol aqueous solution for several times, and drying the centrifuged solid to obtain the cobaltosic oxide nanocube with the surface coated with PDA;
thirdly, calcining the material obtained in the second step to obtain a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure; the calcining condition is that the cobaltosic oxide nanocubes with the surfaces coated with the PDA obtained in the second step are kept at the constant temperature for 3 hours at the temperature rising rate of 5 ℃/min and the temperature of 500 ℃;
in the first step, the mass ratio of cobalt nitrate hexahydrate to sodium hydroxide is 4: 1;
in the second step, the concentration of cobaltosic oxide is 0.9g/mL, and the concentration of dopamine hydrochloride is 0.4 g/mL;
the carbon-coated porous cobaltous oxide nanocube three-dimensional material with the shell-core structure prepared by the preparation method has a plurality of mesopores, and the transmission path of lithium ions and electrons is improved, so that the rate capability of the material is improved.
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CN109888237B (en) * 2019-03-07 2020-12-11 肇庆市华师大光电产业研究院 Sodium-ion battery negative electrode material and preparation method thereof
CN110600712B (en) * 2019-10-08 2021-06-04 西京学院 Carbon and nitrogen Co-doped Co3O4Composite material, preparation method and application thereof
CN111233049A (en) * 2020-01-19 2020-06-05 安徽师范大学 Sulfur-loaded composite material of zinc cobaltate microspheres with multilayer mesoporous structure and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery
CN114105217B (en) * 2021-10-28 2023-11-03 合肥国轩高科动力能源有限公司 Carbon-coated cobaltosic oxide negative electrode material and preparation method and application thereof
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